CN104884162B - Silicon metal phosphate molecular sieve, its preparation method and use - Google Patents

Silicon metal phosphate molecular sieve, its preparation method and use Download PDF

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CN104884162B
CN104884162B CN201380062741.6A CN201380062741A CN104884162B CN 104884162 B CN104884162 B CN 104884162B CN 201380062741 A CN201380062741 A CN 201380062741A CN 104884162 B CN104884162 B CN 104884162B
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mol ratio
ammonium
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CN104884162A (en
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G·J·刘易斯
L·M·奈特
P·雅库布扎克
J·E·斯坦奇克
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Universal Oil Products Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • C10G47/16Crystalline alumino-silicate carriers
    • C10G47/20Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54Phosphates, e.g. APO or SAPO compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66Catalytic processes
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00Reforming naphtha
    • C10G35/04Catalytic reforming
    • C10G35/06Catalytic reforming characterised by the catalyst used
    • C10G35/065Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/08Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/82Phosphates

Abstract

A kind of crystalline microporous metal phosphate for the new type for being named as MAPSO 64 is synthesized.These metal phosphates are represented with empirical formula R+rMmn+EPxSiyOz, wherein R is organoammonium cations (such as ETMA+ or DEDMA+), M is divalent metal (such as alkaline-earth metal or transition metal), and E is backbone element (such as aluminium or gallium).The compositions of micropore MAPSO 64 have BPH topological structures, and have the catalytic performance for being used for implementing various hydrocarbon conversion processes and the separating property for separating at least one component.

Description

Silicon metal phosphate molecular sieve, its preparation method and use
The statement of priority
This application claims the U.S. Patent Application No. 13/689,887 submitted on November 30th, 2012 and in 2012 The priority of the U.S. Patent Application No. submitted November 30 13/689,893 (being US8,569,557 now), these patents The full content of application is incorporated by reference herein.
Technical field
The present invention relates to a kind of electrically charged microporous silicon metal phosphate molecular sieve for the new type for being named as MAPSO-64. They are represented by following empirical formula
R+ rMm n+EPxSiyOz
Wherein M is divalent metal (such as magnesium or zinc), and R is organoammonium cations (such as diethyl-dimethyl ammonium or ethyl Trimethyl ammonium), E is triad (such as aluminium or gallium).
Background technology
Zeolite is crystalline alumino salt composite, and these compositions are micropore and are the AlO shared by angle2 -And SiO2 Tetrahedron is constituted.Many zeolites (both naturally occurring and synthetic preparation) are currently being used in various industrial process.Synthesis Zeolite be by using suitable Si, Al source and structure directing agent (such as alkali metal, alkaline-earth metal, amine or organic ammonium sun from Son) Hydrothermal Synthesiss and prepare.Structure directing agent is present in the hole of zeolite, and mainly cause to ultimately form it is specific Structure.These materials make the skeleton electric charge related to aluminium keep balance, and are also used as space filler.The feature of zeolite It is the channel openings with uniform-dimension, so that with sizable ion exchange capacity, and can not replace significantly Reversibly make the absorption being dispersed in whole crystals space in the case of any atom for constituting permanent zeolite crystal structure Mutually desorb.Zeolite may be used as the catalyst for hydrocarbon conversion reactions, and the hydrocarbon conversion reactions can occur in zeolite On inner surface on outer surface and inside zeolite pores.
The poromerics of other compositions (for example, non-zeolitic composition) can be manufactured using the technology being substantially the same. In nineteen eighty-two, Wilson et al. first reported aluminophosphate molecular sieve (commonly known as AIPO classes), and these molecular sieves are tools There is the poromerics of many performances in these same performances of zeolite, although they are no silica and by AlO2 -With PO2 +Tetrahedron is constituted, referring to US 4,310,440.Then, by using SiO2Tetrahedron replaces PO2 +Tetrahedron and by skeleton electricity Lotus introduces natural aluminate or phosphate to manufacture commonly known as SAPO molecular sieve, referring to US 4440871.Skeleton electric charge is introduced The another method of natural aluminate or phosphate is to use [M2+O2]2-Tetrahedron replaces AlO2 -Tetrahedron, is derived from MeAPO molecular sieves, ginseng See US 4567029.Furthermore, it is possible to by simultaneously by SiO2[M2+O2]2-Tetrahedron introduces skeleton and introduces skeleton electric charge On AIPO based molecular sieves, so that MeAPSO molecular sieves are obtained, as disclosed in US 4973785.
Applicant has synthesized a kind of microporous silicon metal of new type with the MeAPSO compositions for being named as MAPSO-64 Phosphate backbone material.MAPSO-64 materials have BPH topological structures, are accommodated in the topological structure with vertical 8- annular distances slot sytem 12- annular distance slot sytems, see, for example, http://izasc-mirror.la.asu.edu/fmi/xsl/IZA-SC/ftc_ fw.xsl- db=Atlas_main&-lay=fw&-max=25&STC=BPH&-find.For AIPO sills, in the past BPH topological structures are prepared in the MAPO compositions for being referred to as STA-5 material, wherein using three complicated quaternary ammonium salt moulds Plate 1,3,5- tri- (triethyl ammonium methyl) benzene, referring to Patinec et al., Chem.Mater., 11,456-2462 (1999).Phase Instead, micropore MAPSO-64 materials of the invention are additionally contained in the Si in skeleton, and can use structure directing simply too much Agent diethyl-dimethyl ammonium (DEDMA+) or ethyl trimethyl ammonium (ETMA+) and prepare.
The content of the invention
As described above, the present invention relates to a kind of microporous silicon metal tripolyphosphate molecules of salt for the new type for being named as MAPSO-64 Sieve.One embodiment of the invention is a kind of microporous crystalline material, and the microporous crystalline material, which has, includes EO2 -、PO2 +、[M2+ O2]2-And SiO2The three-dimensional framework of tetrahedron element and based on synthesis and the anhydrous experience group represented by following empirical formula Into:
R+ rMm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one skeleton divalent metal, " m " be M and E mol ratio and from 0.01 be changed to 1.5, R be selected from tetramethyl-ammonium (TMA+), ethyl trimethyl ammonium (ETMA+), diethyl-dimethyl ammonium (DEDMA+), choline, oxypropyl trimethyl ammonium (PTMA+), methyl triethyl ammonium (MTEA+), tetraethyl Ammonium (TEA+), dimethyl dipropylammonium (DPDMA+), tetrapropyl ammonium (TPA+) and its mixture organoammonium cations, " r " is R With E mol ratio and with 0.1 to 2.0 value, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P With E mol ratio and being changed to 2.5 from 0.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E Mol ratio and with determined by below equation be worth:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffraction pattern at least with d- spacing and intensity shown in Table A:
Table A
Another embodiment of the invention is the method for preparing above-mentioned crystalline microporous aluminate or phosphate based molecular sieve.Should Method includes the reactant mixture of any one or two formed in reaction source and M and Si comprising R, E, P and at 60 DEG C To heating response mixture at a temperature of 200 DEG C up to being enough to form the period of molecular sieve, the reactant mixture has with following Oxide mol ratio represented by composition:
aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
Wherein " a " has 0.75 to 16 value, and " b " has 0.01 to 3 value, and " c " has 0.8 to 8 value, and " d " has 0.01 to 4 value, " e " has 20 to 800 value.
Yet another embodiment of the present invention is the hydrocarbon conversion process for using above-mentioned molecular sieve as catalyst.The process Including making at least one hydrocarbon be contacted with molecular sieve at conversion conditions to produce at least one inverted hydrocarbon.
Another embodiment of the invention is the separation process using crystallization MAPSO-64 materials.The process may include by The mixture of molecular substance is separated or removes pollutant by making fluid be contacted with MAPSO-64 molecular sieves.Molecule thing The separation of matter can be based on molecular size (kinetic diameter) or the polarity degree based on molecular substance.Can by with molecular sieve Ion exchange and remove pollutant.
Embodiment
Applicant has been prepared for the class microporous silicon metal phosphate material that its structure shows BPH topological structures.The present invention Microporous crystalline material (MAPSO-64) have based on synthesis and the anhydrous experience represented by following empirical formula constitute:
R+ rMm 2+EPxSiyOz
Wherein M is at least one divalent metal selected from alkaline-earth metal and transition metal.The concrete example of M cations Son includes but is not limited to:Beryllium, magnesium, cobalt (II), manganese, zinc, iron (II), nickel and its mixture.R is organoammonium cations, its example Including but not limited to:Choline cation, [(CH3)3N(CH2)2OH]+, tetramethylammonium cation (TMA+), ethyl trimethyl ammonium (ETMA+), trimethylpropylammonium, diethyl-dimethyl ammonium (DEDMA+), methyl triethyl ammonium (MTEA+), trimethylpropylammonium (PTMA+), dimethyl diethanol ammonium, tetraethyl ammonium (TEA+), dimethyl dipropylammonium (DPDMA+), tetrapropyl ammonium (TpA+) and Its mixture, " r " is R and E mol ratio and is changed to 2.0 from 0.1.The value of " m " is M and E mol ratio and from 0.01 1.5 are changed to, " x " is P and E mol ratio and is changed to 2.5 from 0.5." y " represents the ratio of silicon and E and become from 0.01 Change to 1.0.E is the triad of tetrahedral coordination, and it is present in skeleton and selected from aluminium, gallium, iron (III) and boron.Finally, " z " is O and E mol ratio and obtained by below equation:
Z=(2m+r+3+5x+4y)/2.
Microporous crystalline silico metal phosphate material MAPSO-64 is prepared by the hydrothermal crystallization of reactant mixture, described Reactant mixture is prepared by the way that the reaction source of R, E, phosphorus, M and silicon is mixed.When E is aluminium, reaction source is included but not It is limited to:Aluminium-alcohol salt, precipitation method aluminum oxide, aluminum metal, aluminium hydroxide, aluminium salt and alumina sol.The concrete example attached bag of aluminium-alcohol salt Include but be not limited to:Yuanzhong aluminium butoxide (aluminum ortho sec-butoxide) and former aluminium isopropoxide (aluminum ortho isopropoxide).The source of other E elements includes but is not limited to:Organic boronic ammonium, boric acid, precipitation method gallium oxyhydroxide, Gallium sulfate, ferric sulfate and iron chloride.The source of phosphorus includes but is not limited to:Former phosphoric acid (orthophosphoric acid), five oxygen Change two phosphorus and ammonium dihydrogen phosphate.The source of silica includes but is not limited to:Tetraethyl orthosilicate (tetraethylorthosilicate), cataloid and precipitated silica.The source of M metals includes each alkali Halide salts, nitrate, acetate and the sulfate of earth metal and transition metal.R is to be selected from choline, TMA+、ETMA+、DEDMA+、MTEA+、TEA+、TPA+、PTMA+、DPDMA+, dimethyl diethanol ammonium and its mixture organoammonium cations, and it comes Source includes hydroxide, chloride, bromide, iodide and fluoride compound.Specific example includes but is not limited to:Hydroxide Choline and Choline Chloride, ethyl-trimethyl ammonium hydroxide, diethyl-dimethyl ammonium hydroxide, diethyl-dimethyl ammonium chloride, first Base triethylammonium hydroxide and methyl triethyl ammonium chloride.In a specific embodiment, R is DEDMA+.In another reality Apply in scheme, R is ETMA+.In another embodiment, R is DEDMA+With the group of at least one single electric charge organoammonium cations Close, the organoammonium cations are selected from choline, TMA+、ETMA+、MTEA+、PTMA+, dimethyl diethanol ammonium, TEA+、DPDMA+With TPA+.In still another embodiment, R is ETMA+With the combination of at least one single electric charge organoammonium cations, organic ammonium sun Ion is selected from choline, TMA+、DEDMA+、MTEA+、PTMA+、DPDMA+, dimethyl diethanol ammonium, TEA+And TPA+
The reactant mixture of reaction source comprising desired component can be described with the mol ratio of the oxide of following formula:
aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
Wherein " a " is changed to 16 from 0.75, and " b " is changed to 3 from 0.01, and " c " is changed to 8 from 0.8, and " d " changes from 0.01 To 4, " e " is changed to 800 from 20.If using alkoxide, may include distillation or the evaporation step for removing alcohol hydrolysate. Reactant mixture is set to be reacted at a temperature of 60 DEG C to 200 DEG C now, or in another embodiment, at 115 DEG C to 175 Reacted 1 day to 3 weeks at a temperature of DEG C, or in another embodiment, in sealed reaction vessel at autogenous pressures Reaction 1 to 7 day.After the completion of crystallization, solid product is isolated from heterogeneous mixture for example, by filtering or centrifuging, so It is washed with deionized and is dried in atmosphere under up to 100 DEG C of environment temperature afterwards.It is optionally possible to by MAPSO-64 Crystal seed is added in reactant mixture, so as to accelerate the formation of desired microporous compositions.
MAPSO-64 silicon metal tripolyphosphate based materials obtained in said process are characterized at least to have following Table A Shown in d- spacing and relative intensity X-ray diffraction pattern.
Table A
It can adopt and MAPSO-64 is modified in many ways, to adapt it to the use in special-purpose.Change Property include roasting, ammonia roasting, ion exchange, steam treatment, it is various acid extraction, ammonium hexafluorosilicate handle or its any group Close, such as US 6, summarized in 776,975B1 on UZM-4, the full content of the patent document is incorporated by reference this Wen Zhong.Changeable performance includes porosity, absorption property, skeleton composition, acidity, heat endurance etc..
In the MAPSO-64 materials synthesized by it is comprising part, in its hole it is commutative or charge balance sun from Son.These exchangeable cations can be exchanged into other cations, or in the case of organic cation can by Heating under controlled condition and they are removed.Because MAPSO-64 has big 12- annular distance gap BPH topological structures, often may be used Directly to remove small organoammonium cations by ion exchange.In one embodiment, organic sun is removed from hole The method of ion is ammonia roasting.It is calcined in atmosphere and the organic cation in hole is changed into proton, this can for example causes The Al of part is removed from skeleton when exposed to vapor.When implementing roasting in ammonia atmosphere, organic sun in hole from Son is by NH4 +Cation replacement and skeleton remain in that it is perfect, referring to Studies in Surface Science, Volume (2004) the 154th, the 1324-1331 pages.The representative condition being calcined for ammonia includes:Use is flowed with 1.1l/min flow rate Dynamic anhydrous gaseous ammonia, reaches at 5 minutes to 4 hours while making sample be warming up to 500 DEG C and be maintained at the temperature with 2-5 DEG C/min In the range of period.The MAPSO-64 of the ammonium form formed generally has the diffraction pattern in Table A.Then, can be by ammonium The MAPSO-64 ion exchanges of form turn into any other form, so as to be formed with the modification group represented by following empirical formula Into material MAPSO-64M:
M’n p+Mm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one divalent metal, " m " It is M and E mol ratio and is changed to 1.5, M from 0.01 ' it is NH4 +、H+, alkali metal, alkaline-earth metal, transition metal and rare earth gold Category and its mixture, " n " is M ' with E mol ratio and with 0.03 to 2.0 value, and " p " is M ' weighted average price, and E is Triad selected from aluminium, gallium, iron, boron and its mixture, " x " is P and E mol ratio and is changed to 2.0 from 0.5, and " y " is Si and E mol ratio and 1.0 are changed to from 0.01, " z " is O and E mol ratio and with being determined by below equation Value:
Z=(pn+2m+3+5x+4y)/2
And it is characterized in that it has the X-ray diffraction pattern at least with d- spacing and intensity shown in Table A:
Table A
In one embodiment of the invention, MAPSO-64 be up at a temperature of at least 400 DEG C it is heat-staple, MAPSO-64 is heat-staple at a temperature of up at least 500 DEG C in another embodiment.
When air and around be calcined MAPSO-64 in vapor when, have metal (such as Al) from the loss in skeleton, Change X-ray diffraction pattern in X-ray diffraction pattern observed by this MAPSO-64 that can be synthesized from Table A, referring to Studies in Surface Science, volume (2004) the 154th, the 1324-1331 pages.The MAPSO-64 materials of air roasting Material, MAPSO-64C is represented by following empirical formula:
HaMm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one divalent metal, " m " It is M and E mol ratio and to be changed to 1.5, H from 0.01 be proton, " a " is H and E mol ratio and with 0.1 to 2.0 Value, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P and E mol ratio and be changed to from 0.5 2.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E mol ratio and had by below equation It is worth determined by formula:
Z=(a+2m+3+5x+4y)/2
The crystallization MAPSO-64 materials of the present invention can be used for the separation of the mixture of molecular substance, by ion exchange Pollutant removal and the catalysis to various hydrocarbon conversion processes.The separation of molecular substance can (dynamics be straight based on molecular size Footpath) or molecular substance polarity degree.
The MAPSO-64 compositions of the present invention are also used as catalyst or catalyst in various hydrocarbon conversion processes Carrier.Hydrocarbon conversion process is well known in the present art, and including cracking, be hydrocracked, aromatic compound and isomery The alkylation of alkane, isomerization, polymerization, reformation, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, Hydrodenitrogeneration, hydrodesulfurization, methanol change into alkene, methanation and synthesis gas rotation (syngas shift) technique.At these The specific reaction condition and feed type that can be used in technique are set forth in US 4,310,440, US4,440,871 and US 5, 126,308, the content of these patent documents is incorporated by reference herein.It is preferred that hydrocarbon conversion process be wherein hydrogen A kind of process of component, such as hydrotreating or hydrofinishing, hydrogenate, be hydrocracked, hydrodenitrogeneration, hydrodesulfurization.
Hydrocracking condition is typically included in 400 to 1200 °F (204-649 DEG C), preferably 600 to 950 °F (316-510 DEG C) in the range of temperature.Reaction pressure is in the range of air is depressed into 3,500psig (24,132kPa g), preferably 200 Between 3000psig (1379-20,685kPa g).Time of contact is generally corresponded in 0.1hr-1To 15hr-1In the range of, It is preferred that in 0.2 and 3hr-1Between liquid hourly space velocity (LHSV) (LHSV).Hydrogen cycle rate is in 1,000 to 50,000 standard cubic foots (scf)/bucket charging (178-8,888 standards m3/m3) in the range of, preferably fed at 2,000 and 30,000scf/ barrels (355-5, 333 standard m3/m3) between.Suitable hydroprocessing condition is typically in above-mentioned large-scale hydrocracking condition.
Generally reaction zone effluent is discharged from catalyst bed, then separated by partial condensation and vapor-liquid, then It is fractionated to reclaim its various component.By hydrogen and if desired all or part of unconverted heavy material is recycled to instead Answer device.Alternately, can be by two benches flow applications in the unconverted materials just entered in second reactor.The catalysis of the present invention Agent can be only used for it is this during a stage or can be used in two reactor stages.
Preferably by the raw material such as gas oil, heavy naphtha, deasphalted crude residual oil, (wherein gasoline is the main phase Hope product) implement catalytic cracking process using MAPSO-64 compositions.850 to 1100 °F of temperature conditionss, 0.5 to 10 LHSV values and 0 to 50psig pressure condition are suitable.
The alkylation of aromatic compound generally includes to make aromatic compound (C2To C12) it is particularly benzene and monoolefine hair Raw reaction, to manufacture the aromatic compound of straight chained alkyl substitution.The process is the aromatic compound between 5: 1 and 30: 1 Thing:Alkene is (for example, benzene:Alkene) ratio, 0.3 to 6hr-1LHSV, 100 to 250 DEG C of temperature and 200 to 1000psig pressure Implement under power.Further detail below content on device can be found in US 4, and 870,222, the content of the patent document is to refer to Mode is incorporated herein.
Using alkene by isoparaffin alkylation to manufacture the process for the alkylates for being suitable for use as engine fuel component It is the pressure and 0.1 to 120 weight (hourly) space velocity (WHSV) that 6,894kPa (1,000psig) is depressed at a temperature of -30 to 40 DEG C, from air (WHSV) implement under.The detail content being alkylated on alkane can be found in US 5,157,196 and US 5,157,197, and these are special The content of sharp document is incorporated by reference herein.
It is to contact the phase of being consequently formed by making methanol at conversion conditions with MAPSO-64 catalyst that methanol, which changes into alkene, The alkene of prestige and realize.Methanol can be in liquid phase or vapor phase, wherein it is preferred that vapor phase.Methanol is set to be urged with MAPSO-64 The process of agent contact can be carried out using continuation mode or basis, wherein it is preferred that continuation mode.Methanol with The time quantum of MAPSO-64 catalyst contact must be large enough to methanol changing into desired light olefin product.When the process It is that time of contact was changed to 1 hour from 0.001 hour, preferably 0.01 hour to 1.0 small when being carried out using basis When.Longer time of contact is used at a lower temperature, and then uses shorter time of contact at relatively high temperatures.In addition, working as The process is that the weight (hourly) space velocity (WHSV) (WHSV) based on methanol can be from 1hr when being carried out using continuation mode-1It is changed to 1000hr-1, preferably 1hr-1To 100hr-1
In general, the process must be implemented so as to sufficiently fast speed formation light olefin at elevated temperatures. Therefore, the process should be real at a temperature of 300 DEG C to 600 DEG C, preferably 400 DEG C to 550 DEG C, most preferably 450 DEG C to 525 DEG C Apply.The process can include implementing under self-generated pressure under large-scale pressure.Therefore, pressure can change from 0kPa (0psig) To 1724kPa (250psig), preferably 34kPa (5psig) to 345kPa (50psig).
Optionally, methanol feedstock can be diluted with inert diluent and methanol is changed into alkene so as to higher efficiency.Can The example of the diluent used be helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, hydrogen, vapor, alkane (for example Methane), aromatic hydrocarbon (such as benzene, toluene and its mixture).The amount of used diluent can significantly change, typically raw material The % of 5 to 90 moles of %, preferably 25 to 75 moles.
The actual configuration of reaction zone can be any catalyst reaction device known in the art.Therefore, it can be used single anti- The reaction zone for answering area or some serial or parallel connections to arrange.In this reaction zone, make methanol feedstock flowing by accommodating The bed of MAPSO-64 catalyst.When using multiple reaction zones, one or more MAPSO-64 catalyst can be used in series to make Make desired product mixture.Dynamic bed system (for example, fluid bed or moving bed) can be used to replace fixed bed.This dynamic System will promote any regeneration for the MAPSO-64 catalyst that may be may require that., then can be by MAPSO- if necessary to regenerate 64 catalyst are introduced continuously into renewing zone as moving bed, wherein containing carbon materials for example, by the oxidation in oxygen-containing atmosphere to remove Expect and regenerate it.
Embodiment given below is, in order to illustrate the purpose of the present invention, and to be not intended to exceedingly be limited in appended power The general broad scope of the invention that profit is stated in requiring.Product will be named as MeAPSO-64, to reflect composition and tie Structure.
The structure of the MAPSO-64 compositions of the present invention is determined by being analyzed x-ray powder pattern.Under X-ray pattern provided in the embodiment in face is obtained using standard X-ray powder diffraction techniques.Radiation source is in 45kV With the high intensity X-ray tube operated under 35mA.It is by appropriate computer based skill from the alpha-emitting diffraction patterns of copper K- Art and obtain.Flat compressing powder sample is continuously scanned with 2 ° to 56 ° (2 θ).With angstromFor the interplanar of unit Away from (d) obtained from the diffraction maximum position represented by θ, wherein θ is Prague what is observed in the digitalized data Angle.Intensity is determined, " I based on the integral area for subtracting the diffraction maximum after background0" be most strong line or peak intensity, " I " is The intensity at other each peaks.
As will be appreciated by one of skill in the art, the θ of parameter 2 determination can be limited by human error and machine error, Both errors are combined can bring ± 0.4 ° of uncertainty to 2 θ each report value.Certainly, the uncertainty is also found expression in In the report value of d- spacing, the d- spacing is based on 2 θ values and calculated.The inexactness is universal in the art, is e insufficient to Exclude between crystalline material of the present invention and the difference with prior art compositions.The X-ray pattern reported in part In, the relative intensity of d- spacing is represented with mark vs, s, m and w, these marks represent respectively it is very strong, strong, medium and It is weak.In 100 × I/I0Aspect, above-mentioned title is defined as:
W=0-15;M=15-60:S=60-80 and vs=80-100
In some cases, its X-ray powder diffraction figure sample is can refer to determine the purity of sintetics.Thus, for example If claiming that a sample is pure, then intention only represents not to be attributed to crystalline impurities in the X-ray pattern of the sample Line, and be not intended to represent that amorphous materials is not present.
In order to which the present invention is more fully described, and it set forth following examples.It should be understood that these embodiments are to be The purpose of explanation, and it is not intended to exceedingly limit the broad scope of the invention stated in the following claims.
Embodiment 1
100.00g DEDMAOH (20%) are added into polytetrafluoroethylene beaker, are then stirred with super mixer.So Afterwards, 4.65g Al (OH) are little by little added every time under agitation3(78.1%) it is, molten for what is almost clarified until reactant mixture Liquid.Then, 5.94g TEOS (98%) are promptly added using dropper.Reactant mixture is stirred 1.5 hours to be TEOS The chance of hydrolysis is provided.Then, by reactant mixture 12.89g H3PO4(85%) handled, in the period of 15 minutes Inside it is added dropwise and allows to be stirred for 20 minutes, now solution is clarification.Individually, by 20.5g Zn (OAc)2·2H2O is molten Solution is in 10.00g deionized waters.This solution is slowly added drop wise, reactant mixture is still settled solution.It is being allocated in Before in 7 polytetrafluoroethyllining lining autoclaves, reactant mixture is stirred for 1 hour, at autogenous pressures with various temperature Digested with the period.Product is separated and is washed with deionized by centrifuging.By powder x-ray diffraction will from Digested 55 and 152 hours at 150 DEG C and the product at 175 DEG C obtained in the reactant mixture of digestion 55 hours is accredited as ZAPSO-64.The representative diffracted ray of 150 DEG C/152 small phases is shown in following table 1.The elementary analysis of the product has Element ratio C/N=6.38, N/Al=0.40, Zn/Al=0.97, P/Al=1.59, Si/Al=0.16, this and stoichiometry DEDMA0.40Zn0.96AlP1.59Si0.16O6.96Unanimously.
Table 1
Embodiment 2
100.00g ETMAOH (20%) are added into polytetrafluoroethylene beaker to be placed in below high speed agitator.Violent Under stirring, 5.27g Al (OH) are slowly added3(78.1%) and it is made rapidly to dissolve.Then, add in the toppling over of single Plus 6.74g TEOS (98%).In stirring 30 minutes so as to which after TEOS hydrolysis, 14.61g H are added dropwise3PO4(85%).Knot Fruit obtains the solution of clarification.Individually, by 2.32g Zn (OAc)2·2H2O is dissolved in 10.00g deionized waters.By the solution by Drop be added to be still settled solution reactant mixture in.After further homogenize, by reactant mixture distribution 7 In the autoclave of individual polytetrafluoroethyllining lining, digested at autogenous pressures with various temperature and times section.Will by centrifuging Product is separated and is washed with deionized.By powder x-ray diffraction by by the formed product of digestion in 125 DEG C/180 hours It is accredited as MAPSO-64.The representative diffracted ray of the product is shown in following table 2.
Table 2
Embodiment 3
130.00g ETMAOH (20%) and 6.19g cataloids (Ludox are added into polytetrafluoroethylene beaker AS-40,40%SiO2) and stir briefly, then place it into polytetrafluoroethylene (PTFE) bottle and digested 2 hours at 95 DEG C.Make Solution is cooled down, and 6.29g Al (OH) are slowly added with vigorous stirring3(85.1%).Make reactant mixture homogeneous after addition Change 45 minutes and the clarification that remains unchanged, remain in that muddiness.Then, 19.00g H are added dropwise3PO4(85%).Formed Reactant mixture is translucent.Individually, by 1.51g Zn (OAc)2·2H2O is dissolved in 6.0g deionized waters.With dropwise Mode this solution is added in the reactant mixture being stirred vigorously, uniform reactant mixture becomes more during adding It is opaque.In the autoclave that reactant mixture is assigned to 7 polytetrafluoroethyllining linings, at autogenous pressures with various temperature and when Between section digested.Product is separated and is washed with deionized by centrifuging.By powder x-ray diffraction will by 150 DEG C/ The obtained product of digestion is accredited as ZAPSO-64 within 47 hours, but the sample contains a small amount of MAPSO-59 impurity.Following table 3 In show the representative diffracted rays of MAPSO-64 products.
Table 3
Embodiment 4
193.3g DEDMAOH (20%) and 8.12g cataloids (Ludox AS- are added into polytetrafluoroethylene (PTFE) bottle 40,40%SiO2), seal and in an oven in placement 1.5 hours at 100 DEG C.The DEDMA silicate solutions formed are placed in In polytetrafluoroethylene beaker and below high speed agitator.Then, 8.37g Al (OH) are added with vigorous stirring3(83.0%). Then, 24.95g H are added dropwise3PO4(85%), reactant mixture is made further to homogenize.Individually, by 1.98g Zn (OAc)2·2H2O is dissolved in 13.29g deionized waters.The solution is added dropwise in reactant mixture, 30 are further homogenized Minute.Final reactant mixture is transparent white suspension.The reactant mixture of a part is placed in polytetrafluoroethylene (PTFE) Digested 161 hours in the autoclave of lining and at 125 DEG C.Product is separated and is washed with deionized by centrifuging.Pass through The product is accredited as MAPSO-64 by powder x-ray diffraction.The representative diffracted ray of the product is shown in following table 4.
Table 4
Embodiment 5
130.00g ETMAOH (20%) and 6.19g cataloids (Ludox are added into polytetrafluoroethylene beaker AS-40,40%SiO2), mixture is simply stirred, is transferred in polytetrafluoroethylene (PTFE) bottle, is digested 2 hours at 95 DEG C.Will The ETMA silicate solutions formed are placed in beaker and high speed agitator lower section, slowly add 6.29g Al (OH)3 (85.1%) muddy reactant mixture, is formed, or even after 45 minutes after adding and homogenizing.Then, discontinuously with Mode dropwise adds 19.00g H3PO4(85%).Form translucent reactant mixture.Individually, by 3.01gZn (OAc)2·2H2O is dissolved in 12.0g deionized waters.The solution is discontinuously added in the way of dropwise among three parts, simultaneously will Reactant mixture is stirred vigorously.Reactant mixture is still uniform, but becomes opaquer.Reactant mixture is loaded into In the autoclave of 7 polytetrafluoroethyllining linings, digested at autogenous pressures with various temperature and times section.Will by centrifuging Product is separated and is washed with deionized.By powder x-ray diffraction by 125 DEG C/183 hours digestion obtained in production Thing is accredited as MAPSO-64.The representative diffracted ray of the product is shown in following table 5.
Table 5
One embodiment is a kind of with EO2 -、PO2 +、[M2+O2]2-And SiO2The three-dimensional framework of tetrahedron element and The microporous crystalline silico metal phosphate material constituted based on synthesis and the anhydrous experience represented by following empirical formula:
RrM2+ mEPxSiyOz
Wherein M is at least one bivalent cation selected from alkaline-earth metal and transition metal, " m " be M and E mol ratio simultaneously And it is to be selected from choline, tetramethyl-ammonium (TMA to be changed to 1.5, R from 0.01+), ethyl trimethyl ammonium (ETMA+), diethyl-dimethyl Ammonium (DEDMA+), methyl triethyl ammonium (MTEA+), oxypropyl trimethyl ammonium (PTMA+), dimethyl diethanol ammonium, tetraethyl ammonium (TEA+), dipropyl Dimethyl Ammonium (DPDMA+), tetrapropyl ammonium (TPA+) and its mixture organoammonium cations, " r " is rubbing for R and E Value of that than and with 0.1 to 2, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P and E mole Value than and with 0.5 to 2.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E mole Than and be worth determined by below equation:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample.E can be aluminium.M can be selected from magnesium, zinc, cobalt, manganese and its mixture.The silicon metal phosphate material is at up at least 400 DEG C At a temperature of can be Re Wending.The silicon metal phosphate material can be thermally-stabilised at a temperature of up at least 500 DEG C 's.R can be DEDMA+.R can be ETMA+.R can be DEDMA+And TMA+、ETMA+、TEA+、TPA+、DPDMA+, choline, Or PTMA+One kind in cation.R can be ETMA+And TMA+、DEDMA+、TEA+、TPA+、DPDMA+, choline or PTMA+ One kind in cation.
One embodiment includes being used to prepare at least have EO2 -、PO2 +、[M2+O2]2-And SiO2The three of tetrahedron element Dimension skeleton and the microporous crystalline silico metal phosphate material constituted based on synthesis and the anhydrous experience represented by following empirical formula The process of material:
RrMm 2+EPxSiyOz
Wherein M is at least one bivalent cation selected from alkaline-earth metal and transition metal, " m " be M and E mol ratio simultaneously And it is to be selected from choline, tetramethyl-ammonium (TMA to be changed to 1.5, R from 0.01+), ethyl trimethyl ammonium (ETMA+), diethyl-dimethyl Ammonium (DEDMA+), methyl triethyl ammonium (MTEA+), oxypropyl trimethyl ammonium (PTMA+), dimethyl diethanol ammonium, tetraethyl ammonium (TEA+), dipropyl Dimethyl Ammonium (PDMA+), tetrapropyl ammonium (TPA+) cation and its mixture organoammonium cations, " r " be R with E mol ratio and with 0.1 to 2.0 value, E be selected from aluminium, gallium, iron, boron and its mixture triad, " x " be P with E mol ratio and 2.5 are changed to from 0.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E Mol ratio and with determined by below equation be worth:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample, the process includes forming the reactant mixture of the reaction source comprising R, E, P, M and Si and the temperature at 60 DEG C to 200 DEG C Lower heating response mixture to form the period of silicon metal phosphate material up to being enough, and the reactant mixture has with following oxygen Composition represented by the mol ratio of compound:
aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
Wherein " a " has 0.75 to 16 value, and " b " has 0.01 to 3.0 value, and " c " has 0.8 to 8 value, " d " tool There is 0.01 to 4 value, " e " has 20 to 800 value.M can be selected from magnesium, zinc, cobalt, manganese, nickel, iron (II) and its mixture.M's Source can be selected from halide salts, nitrate, acetate, sulfate and its mixture.E source can selected from aluminium isopropoxide, Aluminium secondary butylate, precipitation method aluminum oxide, Al (OH)3, aluminum metal, aluminium salt, boric acid, precipitation method gallium oxyhydroxide, gallium sulfate, sulfuric acid Iron, iron chloride and its mixture.The source of silicon can be selected from tetraethyl orthosilicate, fumed silica, cataloid And precipitated silica.The reactant mixture can be made to react the time up to 1 day to 7 days at a temperature of 125 DEG C to 175 DEG C Section.R can be DEDMA+.R can be ETMA+.R can be DEDMA+With selected from choline, TMA+、ETMA+、MTEA+、PTMA+, two Methyl diethanol ammonium, TEA+、DPDMA+And TPA+At least one organoammonium cations combination.R can be ETMA+With selected from Choline, TMA+、MTEA+、DEDMA+、PTMA+, dimethyl diethanol ammonium, TEA+And TPA+The group of at least one organoammonium cations Close.The process, which may also include, is added to MAPSO-64 crystal seeds in reactant mixture.
One embodiment includes the silicon metal phosphate of modified form, wherein modification may include under ammonia roasting condition Ammonia is calcined, and optionally additional ion exchange, has EO to be formed2 -、PO2 +、[M2+O2]2-And SiO2Tetrahedron element Three-dimensional framework and based on the anhydrous modified microporous silicon metal phosphate constituted represented by following empirical formula, MAPSO- 64M:
M’n p+Mm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+And its at least one divalent metal of mixture Cation, " m " is M and E mol ratio and is changed to 1.5, M from 0.01 ' it is NH4 +、H+, alkali metal, alkaline-earth metal and rare earth Metal and its mixture, " n " is M ' with E mol ratio and with 0.03 to 2.0 value, and " p " is M ' weighted average price, E It is the triad selected from aluminium, gallium, iron, boron and its mixture, " x " is P and E mol ratio and is changed to 2.5 from 0.5, " y " It is Si and E mol ratio and is changed to 1.0 from 0.01, " z " is O and E mol ratio and had by below equation institute really Fixed value:
Z=(pn+2m+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample.
One embodiment includes a kind of crystalline microporous silicon metal phosphate MAPSO-64C of calcined form of stabilization, should Roasting be included under roasting condition heat silicon metal phosphate so as to air and around remove in the presence of vapor organic sun from Son, the MAPSO-64 has the EO represented by following empirical formula2 -、PO2 +、SiO2[M2+O2]2-The three-dimensional of tetrahedron element Skeleton:
HaMm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+And its at least one divalent metal of mixture Cation, " m " is M and E mol ratio and to be changed to 1.0, H from 0.01 be proton, and " a " is H and E mol ratio and had 0.1 to 2.0 value, E be selected from aluminium, gallium, iron, boron and its mixture triad, " x " be P and E mol ratio and from 0.5 is changed to 2.5, and " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E mol ratio and had It is worth determined by below equation:
Z=(a+2m+3+5x+4y)/2.
One embodiment includes hydrocarbon conversion process, and the conversion process makes comprising at least under the conditions of being included in the hydrocarbon conversion A kind of stream of hydrocarbon is contacted with catalyst to produce at least one inverted product, and wherein catalyst is selected from microporous crystalline MAPSO-64 materials, microporous crystalline MAPSO-64M materials, microporous crystalline MAPSO-64C materials or its mixture, wherein MAPSO-64 has EO2 -、PO2 +、[M2+O2]2-And SiO2The three-dimensional framework of tetrahedron element and based on synthesis and it is anhydrous by Experience composition represented by following empirical formula:
RrMm 2+EPxSiyOz
Wherein M is at least one 2+ valencys cation selected from alkaline-earth metal and transition metal, " m " be M and E mol ratio simultaneously And it is to be selected from ethyl trimethyl ammonium (ETMA to be changed to 1.5, R from 0.01+), choline, diethyl-dimethyl ammonium (DEDMA+), propyl group Trimethyl ammonium (PTMA+), tetramethyl-ammonium (TMA+), tetraethyl ammonium (TEA+), dipropyl Dimethyl Ammonium (DPDMA+), tetrapropyl ammonium (TPA+) and its mixture organoammonium cations, " r " be R and E mol ratio and with 0.1 to 2.0 value, E is to be selected from Aluminium, gallium, iron, the triad of boron and its mixture, " x " is P and E mol ratio and is changed to 2.5 from 0.5, " y " be Si with E mol ratio and 1.0 are changed to from 0.01, " z " is O and E mol ratio and with the value determined by below equation:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample;Wherein microporous crystalline MAPSO-64M materials have EO2 -、PO2 +、[M2+O2]2-And SiO2The three-dimensional framework of tetrahedron element with And constituting represented by following empirical formula:
M’n p+Mm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one+divalent metal cation, " m " It is M and E mol ratio and is changed to 1.5, M from 0 ' it is selected from NH4 +、H+, alkali metal, alkaline-earth metal, rare earth metal and its mixing Thing, " n " is M ' with E mol ratio and with 0.03 to 2.0 value, and " p " is M ' weighted average price, E be selected from aluminium, gallium, The triad of iron, boron and its mixture, " x " is P and E mol ratio and is changed to 2.5 from 0.5, and " y " is rubbing for Si and E You compare and are changed to 1.0 from 0.01, and " z " is O and E mol ratio and has the value determined by below equation:
Z=(pn+2m+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample, and wherein microporous crystalline MAPSO-64C materials have the EO represented by following empirical formula2 -、PO2 +、SiO2[M2+O2 ]2-The three-dimensional framework of tetrahedron element:
HaMm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one+divalent metal cation, " m " It is M and E mol ratio and to be changed to 1.5, H from 0.01 be proton, " a " is H and E mol ratio and with 0.1 to 2.0 Value, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P and E mol ratio and be changed to from 0.5 2.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E mol ratio and had by below equation It is worth determined by formula:
Z=(a+2m+3+5x+4y)/2.
Hydrocarbon conversion process can selected from cracking, be hydrocracked, be alkylated, isomerization, polymerization, reformation, hydrogenation, dehydrogenation, Transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrofinishing, hydrodenitrogeneration, hydrodesulfurization, methanol change into alkene Hydrocarbon, methanation, synthesis gas rotation technique, dimerizing olefins, it is oligomeric, dewaxing, and combinations thereof.Hydrocarbon conversion process can be that hydrogenation splits Change or hydrotreating, wherein be hydrocracked or hydrotreating can the temperature in the range of 400 to 1200 °F (204-649 DEG C) and Air is depressed under the pressure in the range of 3,500psig (24,132kPa g) and operated.The process can be in 0.1hr-1To 15hr-1 In the range of liquid hourly space velocity (LHSV) (LHSV) under operate be hydrocracked or hydrotreating.The process can be with 1,000 to 50, 000 standard cubic foot (scf)/bucket charging (178-8,888 standards m3/m3) in the range of hydrogen cycle rate and the hydrogenation that operates Cracking or hydrotreating.The process may also include the effluent for removing and including at least one inverted product, by the effluent point Evaporate, and reclaim at least one unconverted product.The process makes effluent undergo part before may additionally include fractionation cold It is solidifying to be separated with vapor-liquid.The process may also include is recycled to catalyst by least one of effluent.Hydrocarbon conversion process It may include that two benches are operated, and catalyst is present at least one stage in the two stages.Hydrocarbon conversion process can be with It is to operate under temperature in the range of 850 to 1100 °F, 0.5 to 10 LHSV values and pressure in the range of 0 to 50psig Catalytic cracking.Hydrocarbon flow can be selected from gas oil, heavy naphtha and deasphalted crude residual oil.Hydrocarbon conversion process can be virtue The alkylation of fragrant compounds of group, and inverted product can be the aromatic compound of at least one straight chained alkyl substitution, Wherein the process is with the aromatic compound between 5: 1 and 30: 1:Olefin molar ratio, 0.3 to 6hr-1LHSV, 100 to 250 DEG C of temperature and 200 is operated to 1000psig pressure.Hydrocarbon conversion process can be the isoparaffin using alkene Alkylation, and inverted product can be adapted at least one alkylates as engine fuel component;And Wherein the process be -30 to 40 DEG C temperature, air be depressed into 6,894kPa (1,000psig) pressure and 0.1 to 120 Operated under weight (hourly) space velocity (WHSV) (WHSV).Hydrocarbon conversion process can be that methanol changes into alkene, wherein the process be at 300 DEG C extremely Operated under 600 DEG C of temperature and 0kPa (0psig) to 1724kPa (250psig) pressure.Methanol can be in liquid phase or vapor phase In, and it is to use continuation mode or basis to operate.Can be with diluent by methanol dilution, the diluent is selected from helium, argon Gas, nitrogen, carbon monoxide, carbon dioxide, hydrogen, vapor, at least one alkane, at least one aromatic hydrocarbon and its mixing Thing.Catalyst can be located in the one or more catalyst zones arranged with serial or parallel connection construction, and wherein catalyst can With in fixed bed or fluid bed.The process, which may also include, regenerates catalyst.
One embodiment of the invention is a kind of separation process, and the separation process includes making at least two components and material Contact is at least one through separation component to produce, wherein the material is selected from microporous crystalline MAPSO-64 materials, microporous crystalline MAPSO-64M materials, microporous crystalline MAPSO-64C materials or its mixture, wherein MAPSO-64 have EO2 -、PO2 +、[M2+ O2]2- and SiO2The three-dimensional framework of tetrahedron element and based on synthesis and the anhydrous experience group represented by following empirical formula Into:
RrMm 2+EPxSiyOz
Wherein M is at least one 2+ valencys cation selected from alkaline-earth metal and transition metal, " m " be M and E mol ratio simultaneously And it is to be selected from ethyl trimethyl ammonium (ETMA to be changed to 1.5, R from 0.01+), choline, diethyl-dimethyl ammonium (DEDMA+), propyl group Trimethyl ammonium (PTMA+), tetramethyl-ammonium (TMA+), tetraethyl ammonium (TEA+), dipropyl Dimethyl Ammonium (DPDMA+), tetrapropyl ammonium (TPA+) and its mixture organoammonium cations, " r " be R and E mol ratio and with 0.1 to 2.0 value, E is to be selected from Aluminium, gallium, iron, the triad of boron and its mixture, " x " is P and E mol ratio and is changed to 2.5 from 0.5, " y " be Si with E mol ratio and 1.0 are changed to from 0.01, " z " is O and E mol ratio and with the value determined by below equation:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample;Microporous crystalline MAPSO-64M materials have EO2 -、PO2 +And [M2+O2]2-And SiO2In tetrahedron element at least one Three-dimensional framework and constituting represented by following empirical formula:
M’n p+Mm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one+divalent metal cation, " m " It is M and E mol ratio and is changed to 1.5, M from 0.01 ' it is selected from NH4 +、H+, alkali metal, alkaline-earth metal, rare earth metal and its mixed Compound, " n " is M ' with E mol ratio and with 0.03 to 2.0 value, and " p " is M ' weighted average price, E be selected from aluminium, Gallium, iron, the triad of boron and its mixture, " x " is P and E mol ratio and is changed to 2.5 from 0.5, and " y " is Si and E Mol ratio and 1.0 are changed to from 0.01, " z " is O and E mol ratio and with the value determined by below equation:
Z=(pn+2m+3+5x+4y)/2
And it is characterized in that it has the X-ray diffractogram at least with d- spacing and intensity above shown in Table A Sample;And microporous crystalline MAPSO-64C materials have the EO represented by following empirical formula2 -、PO2 +、[M2+O2]2-And SiO2Four The three-dimensional framework of face body unit:
HaMm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+At least one+divalent metal cation, " m " It is M and E mol ratio and to be changed to 1.5, H from 0.01 be proton, " a " is H and E mol ratio and with 0.1 to 2.0 Value, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P and E mol ratio and be changed to from 0.5 2.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E mol ratio and had by below equation It is worth determined by formula:
Z=(a+2m+3+5x+4y)/2.
Separation can the molecular size based on component, the polarity degree of component or component and the ion friendship of the material Change.

Claims (10)

1. one kind has EO2 -、PO2 +、[M2+O2]2-And SiO2The three-dimensional framework of tetrahedron element and based on synthesis and it is anhydrous by The microporous crystalline silico metal phosphate material that experience represented by following empirical formula is constituted:
RrM2+ mEPxSiyOz
Wherein M is at least one bivalent cation selected from alkaline-earth metal and transition metal, " m " be M and E mol ratio and from 0.01 be changed to 1.5, R be selected from choline, tetramethyl-ammonium (TMA+), ethyl trimethyl ammonium (ETMA+), diethyl-dimethyl ammonium (DEDMA+), methyl triethyl ammonium (MTEA+), oxypropyl trimethyl ammonium (PTMA+), dimethyl diethanol ammonium, tetraethyl ammonium (TEA+), dipropyl Dimethyl Ammonium (DPDMA+), tetrapropyl ammonium (TPA+) and its mixture organoammonium cations, " r " is rubbing for R and E Value of that than and with 0.1 to 2, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P and E mole Value than and with 0.5 to 2.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E mole Than and be worth determined by below equation:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffraction pattern at least with d- spacing and intensity shown in Table A:
Table A
2. microporous crystalline silico metal phosphate material according to claim 1, wherein E is aluminium and wherein M be selected from magnesium, Zinc, cobalt, manganese and its mixture.
3. microporous crystalline silico metal phosphate material according to claim 1, wherein R is DEDMA+Or R is ETMA+
4. microporous crystalline silico metal phosphate material according to claim 1, wherein R is EDMA+And TMA+、ETMA+、 TEA+、TPA+、DPDMA+, choline or PTMA+One kind in cation, or wherein R are ETMA+And TMA+、DEDMA+、TEA+、TPA+、DPDMA+, choline or PTMA+One kind in cation.
5. one kind, which is used to prepare, has at least EO2 -、PO2 +、[M2+O2]2-And SiO2The three-dimensional framework of tetrahedron element and based on conjunction Into the method for the microporous crystalline silico metal phosphate material constituted with the anhydrous experience represented by following empirical formula:
RrMm 2+EPxSiyOz
Wherein M is at least one bivalent cation selected from alkaline-earth metal and transition metal, " m " be M and E mol ratio and from 0.01 be changed to 1.5, R be selected from choline, tetramethyl-ammonium (TMA+), ethyl trimethyl ammonium (ETMA+), diethyl-dimethyl ammonium (DEDMA+), methyl triethyl ammonium (MTEA+), oxypropyl trimethyl ammonium (PTMA+), dimethyl diethanol ammonium, tetraethyl ammonium (TEA+), dipropyl Dimethyl Ammonium (DPDMA+), tetrapropyl ammonium (TPA+) cation and its mixture organoammonium cations, " r " is R With E mol ratio and with 0.1 to 2.0 value, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P With E mol ratio and being changed to 2.5 from 0.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, and " z " is O and E Mol ratio and with determined by below equation be worth:
Z=(2m+r+3+5x+4y)/2
And it is characterized in that it has the X-ray diffraction pattern at least with d- spacing and intensity shown in Table A:
Table A
Methods described includes forming the reactant mixture of the reaction source comprising R, E, P, M and Si and the temperature at 60 DEG C to 200 DEG C The degree lower heating reactant mixture to form the period of the silicon metal phosphate material, the reactant mixture tool up to being enough Composition represented by the mol ratio of useful following oxide:
aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
Wherein " a " has 0.75 to 16 value, and " b " has 0.01 to 3.0 value, and " c " has 0.8 to 8 value, and " d " has 0.01 to 4 value, " e " has 20 to 800 value.
6. the microporous crystalline silico metal phosphate material according to claim 1 of a kind of modified form, wherein the modification It is included in ammonia roasting and optionally additional ion exchange under ammonia roasting condition, there is EO to be formed2 -、PO2 +、[M2+O2]2- And SiO2The three-dimensional framework of tetrahedron element and based on the anhydrous modified micropore silicon metal constituted represented by following empirical formula Phosphate, MAPSO-64M:
M’n p+Mm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+And its mixture at least one divalent metal sun from Son, " m " is M and E mol ratio and is changed to 1.5, M from 0.01 ' it is NH4 +、H+, alkali metal, alkaline-earth metal and rare earth metal And its mixture, " n " is M ' with E mol ratio and with 0.03 to 2.0 value, and " p " is M ' weighted average price, and E is choosing From the triad of aluminium, gallium, iron, boron and its mixture, " x " is P and E mol ratio and is changed to 2.5 from 0.5, and " y " is Si With E mol ratio and being changed to 1.0 from 0.01, " z " is O and E mol ratio and with determined by below equation Value:
Z=(pn+2m+3+5x+4y)/2
And it is characterized in that it has the X-ray diffraction pattern at least with d- spacing and intensity shown in Table A:
Table A
7. the microporous crystalline silico metal phosphate material according to claim 1 of a kind of calcined form, wherein the roasting Be included under roasting condition by silicon metal phosphate according to claim 1 heating so as to air and around vapor deposit The organic cation is removed so as to form MAPSO-64C lower, and the MAPSO-64C has represented by following empirical formula EO2 -、PO2 +、SiO2[M2+O2]2-The three-dimensional framework of tetrahedron element:
HaMm 2+EPxSiyOz
Wherein M is to be selected from Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+And its mixture at least one divalent metal sun from Son, " m " is M and E mol ratio and to be changed to 1.0, H from 0.01 be proton, and " a " is H and E mol ratio and with 0.1 To 2.0 value, E is the triad selected from aluminium, gallium, iron, boron and its mixture, and " x " is P and E mol ratio and become from 0.5 Change to 2.5, " y " is Si and E mol ratio and is changed to 1.0 from 0.01, " z " is O and E mol ratio and had by following It is worth determined by equation:
Z=(a+2m+3+5x+4y)/2.
8. a kind of method for making charging be contacted with the microporous crystalline silico metal phosphate material according to claim 1,6 or 7, Wherein methods described is hydrocarbon conversion process or separation process.
9. method according to claim 8, wherein the hydrocarbon conversion process be selected from cracking, it is alkylation, isomerization, poly- Conjunction, reformation, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, methanol change into alkene, synthesis gas Rotation technique, dewaxing, and combinations thereof, or wherein described molecular size of the separation process based on component, the polarity degree of component, Or component and the ion exchange of the material.
10. method according to claim 9, wherein the hydrocarbon conversion process be selected from be hydrocracked, hydrofinishing, hydrogenation Denitrogenation, hydrodesulfurization, methanation, dimerizing olefins, oligomeric and combinations thereof.
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CN109071243A (en) * 2016-04-28 2018-12-21 庄信万丰股份有限公司 STA-20, a kind of recruit's sieve framework-type, preparation method and purposes
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US10449526B2 (en) * 2016-05-25 2019-10-22 Uop Llc High charge density metallophosphate molecular sieves
US10662069B2 (en) * 2018-06-21 2020-05-26 Uop Llc Crystalline metallophosphates, their method of preparation, and use
US10336622B1 (en) * 2018-06-22 2019-07-02 Uop Llc Crystalline metallophosphates, their method of preparation, and use
US10280089B1 (en) * 2018-06-22 2019-05-07 Uop Llc Crystalline metallophosphates, their method of preparation, and use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
CN1549793A (en) * 2000-11-03 2004-11-24 �Ʒ� UZM-5, UZM-5p and UZM-6: crystalline aluminosilicate zeolites and processes using the same
CN1997593A (en) * 2004-04-20 2007-07-11 环球油品公司 UZM-8 and UZM-8HS crystalline aluminosilicate zeolitic compositions and processes using the same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4567029A (en) * 1983-07-15 1986-01-28 Union Carbide Corporation Crystalline metal aluminophosphates
US4744970A (en) * 1984-04-13 1988-05-17 Union Carbide Corporation Cobalt-aluminum-phosphorus-silicon-oxide molecular sieves
US4973785A (en) * 1984-04-13 1990-11-27 Uop Molecular sieve compositions
US4935216A (en) * 1984-04-13 1990-06-19 Uop Zinc-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US5200187A (en) * 1991-09-18 1993-04-06 Exxon Research And Engineering Company Molybdenum phosphate compositions
DE60141057D1 (en) * 2000-04-06 2010-03-04 Dalian Chemical Physics Inst molecular sieves
US6388159B1 (en) * 2000-11-03 2002-05-14 Uop Llc Xylene isomerization process using UZM-5 and UZM-6 zeolites
US6613302B1 (en) * 2000-11-03 2003-09-02 Uop Llc UZM-5, UZM-5P and UZM-6: crystalline aluminosilicate zeolites and processes using the same
US20120157741A1 (en) * 2010-12-17 2012-06-21 Guang Cao Synthesis of Silicoaluminophosphate Having Lev Framework-Type
US8569558B1 (en) * 2012-11-30 2013-10-29 Uop Llc Metallophosphate molecular sieves, method of preparation and use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
CN1549793A (en) * 2000-11-03 2004-11-24 �Ʒ� UZM-5, UZM-5p and UZM-6: crystalline aluminosilicate zeolites and processes using the same
CN1997593A (en) * 2004-04-20 2007-07-11 环球油品公司 UZM-8 and UZM-8HS crystalline aluminosilicate zeolitic compositions and processes using the same

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